CN110982016B - Environment-friendly high-performance hydrolysis-resistant and aging-resistant TPR (thermal Plastic rubber) treating agent grafted through composite - Google Patents
Environment-friendly high-performance hydrolysis-resistant and aging-resistant TPR (thermal Plastic rubber) treating agent grafted through composite Download PDFInfo
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 79
- 230000007062 hydrolysis Effects 0.000 title claims abstract description 19
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 19
- 230000032683 aging Effects 0.000 title claims abstract description 14
- 229920001971 elastomer Polymers 0.000 title abstract description 25
- 239000005060 rubber Substances 0.000 title abstract description 24
- 239000002131 composite material Substances 0.000 title abstract description 13
- 229920003023 plastic Polymers 0.000 title description 2
- 239000004033 plastic Substances 0.000 title description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 81
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims abstract description 66
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims abstract description 58
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000003756 stirring Methods 0.000 claims abstract description 47
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims abstract description 40
- 235000019400 benzoyl peroxide Nutrition 0.000 claims abstract description 40
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims abstract description 29
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims abstract description 29
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 229920003048 styrene butadiene rubber Polymers 0.000 claims abstract description 25
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229920001084 poly(chloroprene) Polymers 0.000 claims abstract description 23
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 63
- 238000011282 treatment Methods 0.000 claims description 32
- 239000003963 antioxidant agent Substances 0.000 claims description 23
- 230000003078 antioxidant effect Effects 0.000 claims description 23
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 claims description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- NTXGQCSETZTARF-UHFFFAOYSA-N buta-1,3-diene;prop-2-enenitrile Chemical compound C=CC=C.C=CC#N NTXGQCSETZTARF-UHFFFAOYSA-N 0.000 abstract description 13
- 239000002904 solvent Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 9
- 239000000178 monomer Substances 0.000 abstract description 9
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 18
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 11
- 230000001070 adhesive effect Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000003999 initiator Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000004383 yellowing Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000036541 health Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000003878 thermal aging Methods 0.000 description 3
- 239000004709 Chlorinated polyethylene Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- SXWIAEOZZQADEY-UHFFFAOYSA-N 1,3,5-triphenylbenzene Chemical compound C1=CC=CC=C1C1=CC(C=2C=CC=CC=2)=CC(C=2C=CC=CC=2)=C1 SXWIAEOZZQADEY-UHFFFAOYSA-N 0.000 description 1
- -1 120# Chemical compound 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
- C08F2/06—Organic solvent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/04—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to rubbers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The invention discloses an environment-friendly high-performance hydrolysis-resistant and aging-resistant TPR treating agent through composite grafting, and relates to a surface treating agent. The raw material components of the treating agent mainly comprise styrene-butadiene rubber, butadiene-acrylonitrile rubber, chloroprene rubber, acetone, butanone, methylcyclohexane, ethyl acetate, dimethyl carbonate, No. 120, methyl methacrylate, tripropylene glycol diacrylate, dibenzoyl peroxide and a terminator. The preparation method mainly comprises the steps of mixing and stirring butanone and methylcyclohexane and the like, adding butadiene styrene rubber, dibenzoyl peroxide and the like, then dropwise adding methyl methacrylate for reaction, adding tripropylene glycol diacrylate and dibenzoyl peroxide, cooling, adding a terminator, 120# and the like, and stirring to obtain the TPR treating agent. The preparation method adopts a method of active monomer composite grafting and uses a weak solvent for reaction, and the obtained treating agent treated TPR shoe material has hydrolysis resistance and aging resistance under the condition of ensuring the bonding performance.
Description
Technical Field
The invention relates to a surface treating agent, in particular to an environment-friendly high-performance hydrolysis-resistant aging-resistant TPR treating agent through composite grafting.
Background
According to statistics, China is the biggest shoe manufacturing base in the world, the shoe manufacturing amount accounts for 70% of the world, and the shoe manufacturing method is the biggest export country of shoes in the world. A large amount of adhesives are used in the manufacturing process of shoes, adhesives of toxic solvents (such as toluene, methylene chloride, halogenated substances and the like) are mostly used in the adhesives on the market at present, the health of people is seriously affected, and the environment is also seriously polluted, so the content of harmful substances of the adhesives must be limited, and a healthy living environment is created for manufacturers and users.
The TPR shoe material is a nonpolar material containing a large amount of mineral oil, cannot be directly adhered by using an adhesive, and must be subjected to surface treatment by using a TPR treatment agent, and the traditional TPR shoe material has high TPR content purity and is easy to treat, can use chloroprene rubber, toluene and the like, and seriously harms the body health of a user. Therefore, researchers have studied TPR treating agents without triphenylbenzene, which are friendly to the environment and users, but at present, the treating agents have the problems of insufficient modification, poor adhesion, serious light reflection effect of TPR shoe materials treated by the TPR treating agents, and the like.
CN103396748B discloses a benzene-free and halogen-free environment-friendly SBS graft modification adhesive and a preparation method thereof. The adhesive comprises SBS792, environment-friendly solvent, grafting monomer, initiator, molecular weight regulator, terminator and tackifying resin. The preparation method comprises the steps of mixing and dissolving SBS792, an initiator, a molecular weight regulator and an environment-friendly solvent, then preparing a grafting monomer mixture, finally adding a terminator to terminate the reaction, then adding tackifying resin, cooling and discharging to obtain the SBS graft modification adhesive. Wherein, the initiator can be dibenzoyl peroxide, the environment-friendly solvent contains 120# gasoline, and the grafting monomer contains methyl methacrylate. Experimental results show that the solid content of a sample prepared by the optimal embodiment is 44.64%, the bonding strength is 6.81N/mm, the thermal aging resistance (7d bonding strength) is 6.94N/mm, the sample has good bonding strength, good heat resistance, environmental protection and low toxicity, but the preparation process is complex, the preparation condition is strict, and large-scale industrial production cannot be carried out.
CN103304750B discloses a method for producing a TPR shoe material surface treating agent. Adding an organic solvent, an SBS elastomer, high chlorinated polyethylene and chlorinated rubber into a reaction kettle, heating, adding MMA and an initiator for reaction, then adding a monomer BA12 and the initiator for reaction, finally adding a terminator, cooling and discharging to obtain a TPR treating agent semi-finished product, and then mixing the organic solvent to adjust the viscosity to be 30-50cps/25 ℃ to obtain a treating agent finished product. The finished product obtained by the preparation method has the advantages of improving the heat resistance and yellowing resistance of the treating agent, but the preparation method uses toxic high chlorinated polyethylene and chlorinated rubber, thereby not only polluting the environment, but also having serious influence on the health of people.
Jin Shaolin discloses a study of a triphenyl-free TPR (thermoplastic rubber) shoe material surface treating agent (jin Shaolin. study of triphenyl-free TPR shoe material surface treating agent [ J ]. chemical engineering and equipment, 2002 (4).). The article discusses the influence of solvent, dibenzoyl peroxide amount, monomer (MMA + BA) amount and MMA/BA ratio on the final product, and summarizes the best experiment, the initial adhesion of the finally prepared triphenylTPR-free treating agent is 2.60KN/m, and the adhesive strength (24h) is 5.40KN/m (bonded material PVC/TPR base). However, the treatment agent prepared by the method has the defects of poor heat resistance, difficult rolling and the like.
In order to research a non-toxic environment-friendly treating agent with good treating effect, research and development personnel have conducted a lot of research, and the currently used TPR treating agent on the market also has the problems of low adhesive strength, poor heat resistance, generation of light reflection marks during treatment, non-compliance with the requirements of environment-friendly use and the like, so that the need for providing a non-toxic environment-friendly TPR treating agent with weak light reflection marks and high adhesive strength during treatment is urgently needed.
Disclosure of Invention
Aiming at the defects and the defects of the existing TPR treating agent, the weak solvent can better meet the requirements, and the triphenyl-free environment-friendly solvent is prepared by selecting a proper mixed solvent ratio, dibenzoyl peroxide amount and monomer ratio from the triphenyl-free mixed solvent and synthesizing the SBS grafted methyl methacrylate/tripropylene glycol diacrylate terpolymer, and has excellent bonding performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
an environment-friendly high-performance hydrolysis-resistant aging-resistant TPR treating agent grafted compositely comprises the following raw materials: styrene butadiene rubber, butadiene cyanide rubber, chloroprene rubber, acetone, butanone, methylcyclohexane, ethyl acetate, dimethyl carbonate, 120#, methyl methacrylate, tripropylene glycol diacrylate, dibenzoyl peroxide and a terminator.
Further, the TPR treating agent comprises the following raw materials in parts by weight: 50-90 parts of styrene-butadiene rubber, 40-70 parts of butadiene-acrylonitrile rubber, 80-100 parts of chloroprene rubber, 30-70 parts of acetone, 230 parts of butanone 170-.
Furthermore, the weight ratio of the butanone to the methylcyclohexane to the ethyl acetate is 1:2.5-4.0: 1.5-2.1.
Further, the weight ratio of the dimethyl carbonate to the 120# is 1.5-2.0: 1.
Preferably, the TPR treatment agent comprises the following raw materials in parts by weight: 55-80 parts of styrene-butadiene rubber, 50-60 parts of butadiene-acrylonitrile rubber, 80-100 parts of chloroprene rubber, 40-60 parts of acetone, 220 parts of butanone 180-.
Further preferably, the TPR treatment agent comprises the following raw materials in parts by weight: 60 parts of styrene-butadiene rubber, 50 parts of butadiene-acrylonitrile rubber, 90 parts of chloroprene rubber, 50 parts of acetone, 200 parts of butanone, 630 parts of methylcyclohexane, 400 parts of ethyl acetate, 560 parts of dimethyl carbonate, 120#320 parts of methyl methacrylate, 25 parts of tripropylene glycol diacrylate, 0.8 part of dibenzoyl peroxide and 2.0 parts of terminator.
Further, the terminator is one or more of antioxidant BHT, antioxidant 1076, antioxidant B215, antioxidant B225, antioxidant 245, antioxidant 1098 and antioxidant 1010, and is preferably antioxidant BHT.
The invention also provides a preparation method of the TPR treating agent, which comprises the following steps:
(1) firstly, mixing and stirring butanone, ethyl acetate and methylcyclohexane to obtain a mixture 1;
(2) adding styrene butadiene rubber, butadiene cyanide rubber and chloroprene rubber into the mixture 1 obtained in the step (1) and stirring to obtain a mixture 2;
(3) adding dibenzoyl peroxide into the mixture 2 obtained in the step (2), stirring, and then dropwise adding methyl methacrylate to react to obtain a mixture 3;
(4) adding tripropylene glycol diacrylate and dibenzoyl peroxide into the mixture 3 obtained in the step (3) and stirring to obtain a mixture 4;
(5) and (4) cooling the mixture 4 obtained in the step (4), adding a terminator, dimethyl carbonate, 120# and acetone, and stirring to obtain the TPR treating agent.
Further, the stirring speed in the step (1) is 350-450 rpm, and the time is 10-15 minutes.
Further, the stirring speed in the step (2) is 550-750 rpm, the temperature is 51-59 ℃, and the time is 2-4 hours.
Further, the stirring speed in the step (3) is 30-70 r/min, the temperature is 72-88 ℃, and the time is 15 min; the dropping time is 0.5 hour, and the reaction time is 1.5-3 hours.
Further, dibenzoyl peroxide is added in the step (3) in an amount of 0.2 to 0.6 parts by weight.
Further, the stirring speed in the step (4) is 30-70 r/min, the temperature is 72-88 ℃, and the time is 0.5-2 hours.
Further, dibenzoyl peroxide is added in the step (4) in an amount of 0.2 to 0.9 parts by weight.
Wherein, the reaction is considered to be finished when the viscosity of the mixture 4 reaches 2000-3000cps in the step (4).
Further, the temperature of the temperature reduction in the step (5) is 25-50 ℃, the stirring speed is 90-150 r/min, and the time is 1-1.5 hours.
Compared with the prior art, the invention has the beneficial effects that:
(1) the invention prepares an environment-friendly high-performance hydrolysis-resistant aging-resistant TPR treating agent through composite grafting, and prepares a triphenyl-free solvent by selecting a proper mixed solvent proportion, dibenzoyl peroxide dosage, monomer proportion and a terpolymer of synthetic rubber grafted methyl methacrylate/tripropylene glycol diacrylate from the triphenyl-free mixed solvent.
(2) The TPR treating agent prepared by the invention has good hydrolysis resistance and aging resistance.
(3) The solvent used in the invention is different from the traditional solvent, butanone can promote the atmosphere effect in the tank, and methylcyclohexane can improve the conversion rate of the grafting reaction and the rubber dissolving capacity.
(4) The invention uses the solvent without benzene, toluene and xylene, the obtained product can reach higher environmental protection requirement, and the finished product is superior to the common grafting TPR treating agent in various physical indexes by adopting the method of active monomer composite grafting in the preparation process.
(5) The invention effectively improves the comprehensive performance of the product by composite graft multi-copolymerization and has wide application range.
Detailed Description
For a better understanding of the present invention, the present invention is further described in conjunction with the following specific examples, wherein the terminology used in the examples is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. All the raw materials used in the present application are common commercially available products, and thus the source thereof does not need to be particularly limited.
Example 1 an environmentally friendly high performance hydrolysis and aging resistant TPR treatment agent by composite grafting
The TPR treating agent provided by the embodiment is composed of the following raw materials in parts by weight: 50 parts of styrene-butadiene rubber, 40 parts of butadiene-acrylonitrile rubber, 80 parts of chloroprene rubber, 30 parts of acetone, 170 parts of butanone, 500 parts of methylcyclohexane, 300 parts of ethyl acetate, 500 parts of dimethyl carbonate, 250 parts of 120#, 100 parts of methyl methacrylate, 20 parts of tripropylene glycol diacrylate, 0.5 part of dibenzoyl peroxide and 1.5 parts of antioxidant BHT.
The preparation method of the TPR treating agent comprises the following steps:
(1) firstly, butanone, ethyl acetate and methylcyclohexane are mixed and stirred at the stirring speed of 350 revolutions per minute for 10 minutes to obtain a mixture 1;
(2) adding styrene butadiene rubber, chloroprene rubber and butadiene-acrylonitrile rubber into the mixture 1 obtained in the step (1) and stirring at the speed of 550 revolutions per minute at the temperature of 51 ℃ for 2 hours to obtain a mixture 2;
(3) adding 0.3 part of dibenzoyl peroxide into the mixture 2 obtained in the step (2), stirring at the speed of 30 revolutions per minute and the temperature of 72 ℃ for 15 minutes, then dropwise adding methyl methacrylate for reaction, wherein the dropwise adding time is 0.5 hour and the reaction time is 1.5 hours, and obtaining a mixture 3;
(4) adding tripropylene glycol diacrylate and 0.2 part of dibenzoyl peroxide into the mixture 3 obtained in the step (3), stirring at the speed of 30 revolutions per minute at the temperature of 72 ℃ for 1 hour to obtain a mixture 4, and considering that the reaction is finished when the viscosity of the mixture 4 reaches 2000 cps;
(5) and (3) cooling the mixture 4 obtained in the step (4) to 25 ℃, adding antioxidant BHT, dimethyl carbonate, 120# and acetone, and stirring at the speed of 90 revolutions per minute for 1 hour to obtain the TPR treating agent.
Example 2 an environmentally friendly high performance hydrolysis and aging resistant TPR treatment agent by composite grafting
The TPR treating agent provided by the embodiment is composed of the following raw materials in parts by weight: 90 parts of styrene-butadiene rubber, 70 parts of butadiene-acrylonitrile rubber, 100 parts of chloroprene rubber, 70 parts of acetone, 230 parts of butanone, 700 parts of methylcyclohexane, 500 parts of ethyl acetate, 600 parts of dimethyl carbonate, 390 parts of No. 120, 150 parts of methyl methacrylate, 30 parts of tripropylene glycol diacrylate, 1.5 parts of dibenzoyl peroxide and 2.5 parts of antioxidant BHT.
The preparation method of the TPR treating agent comprises the following steps:
(1) firstly, butanone, ethyl acetate and methylcyclohexane are mixed and stirred at the stirring speed of 450 revolutions per minute for 15 minutes to obtain a mixture 1;
(2) adding styrene butadiene rubber into the mixture 1 obtained in the step (1) and stirring at the speed of 750 revolutions per minute and the temperature of 59 ℃ for 4 hours to obtain a mixture 2;
(3) adding 0.6 part of dibenzoyl peroxide into the mixture 2 obtained in the step (2), stirring at the speed of 70 revolutions per minute and the temperature of 88 ℃ for 15 minutes, then dropwise adding methyl methacrylate for reaction, wherein the dropwise adding time is 0.5 hour and the reaction time is 3 hours, and obtaining a mixture 3;
(4) adding tripropylene glycol diacrylate and 0.9 part of dibenzoyl peroxide into the mixture 3 obtained in the step (3), stirring at the speed of 70 r/min at the temperature of 88 ℃ for 1.5 hours to obtain a mixture 4, and considering that the reaction is finished when the viscosity of the mixture 4 reaches 3000 cps;
(5) and (3) cooling the mixture 4 obtained in the step (4) to 50 ℃, adding antioxidant BHT, dimethyl carbonate, 120# and acetone, and stirring at the speed of 150 revolutions per minute for 1.5 hours to obtain the TPR treating agent.
Example 3 Environment-friendly high-performance hydrolysis-resistant aging-resistant TPR treating agent by composite grafting
The TPR treating agent provided by the embodiment is composed of the following raw materials in parts by weight: 55 parts of styrene-butadiene rubber, 50 parts of butadiene-acrylonitrile rubber, 80 parts of chloroprene rubber, 40 parts of acetone, 180 parts of butanone, 550 parts of methylcyclohexane, 350 parts of ethyl acetate, 500 parts of dimethyl carbonate, 250 parts of 120#, 110 parts of methyl methacrylate, 22 parts of tripropylene glycol diacrylate, 0.6 part of dibenzoyl peroxide and 1.5 parts of antioxidant BHT.
The preparation method of the TPR treating agent comprises the following steps:
(1) firstly, butanone, ethyl acetate and methylcyclohexane are mixed and stirred at the stirring speed of 38 revolutions per minute for 12 minutes to obtain a mixture 1;
(2) adding styrene butadiene rubber, chloroprene rubber and butadiene-acrylonitrile rubber into the mixture 1 obtained in the step (1) and stirring at the speed of 590 rpm at the temperature of 53 ℃ for 2.5 hours to obtain a mixture 2;
(3) adding 0.2 part of dibenzoyl peroxide into the mixture 2 obtained in the step (2), stirring at the speed of 40 revolutions per minute and the temperature of 80 ℃ for 15 minutes, then dropwise adding methyl methacrylate for reaction, wherein the dropwise adding time is 0.5 hour and the reaction time is 2 hours, and obtaining a mixture 3;
(4) adding tripropylene glycol diacrylate and 0.4 part of dibenzoyl peroxide into the mixture 3 obtained in the step (3), stirring at the speed of 40 revolutions per minute at the temperature of 80 ℃ for 1.3 hours to obtain a mixture 4, and considering that the reaction is finished when the viscosity of the mixture 4 reaches 2000 cps;
(5) and (3) cooling the mixture 4 obtained in the step (4) to 30 ℃, adding antioxidant BHT, dimethyl carbonate, 120# and acetone, and stirring at the speed of 100 revolutions per minute for 1.2 hours to obtain the TPR treating agent.
Example 4 an environmentally friendly high performance hydrolysis and aging resistant TPR treatment agent by composite grafting
The TPR treating agent provided by the embodiment is composed of the following raw materials in parts by weight: 80 parts of styrene-butadiene rubber, 60 parts of butadiene-acrylonitrile rubber, 90 parts of chloroprene rubber, 60 parts of acetone, 220 parts of butanone, 650 parts of methylcyclohexane, 450 parts of ethyl acetate, 580 parts of dimethyl carbonate, 120#340 parts, 130 parts of methyl methacrylate, 20 parts of tripropylene glycol diacrylate, 1.3 parts of dibenzoyl peroxide and 2.2 parts of antioxidant BHT.
The preparation method of the TPR treating agent comprises the following steps:
(1) firstly, butanone, ethyl acetate and methylcyclohexane are mixed and stirred at the stirring speed of 420 revolutions per minute for 10 minutes to obtain a mixture 1;
(2) adding styrene butadiene rubber into the mixture 1 obtained in the step (1) and stirring at the speed of 720 r/min at the temperature of 57 ℃ for 2-4 hours to obtain a mixture 2;
(3) adding 0.5 part of dibenzoyl peroxide into the mixture 2 obtained in the step (2), stirring at the speed of 60 revolutions per minute and the temperature of 86 ℃ for 15 minutes, then dropwise adding methyl methacrylate for reaction, wherein the dropwise adding time is 0.5 hour and the reaction time is 2.8 hours, and obtaining a mixture 3;
(4) adding tripropylene glycol diacrylate and 0.4 part of dibenzoyl peroxide into the mixture 3 obtained in the step (3), stirring at the speed of 60 revolutions per minute and the temperature of 86 ℃ for 2 hours to obtain a mixture 4, and determining that the reaction is finished when the viscosity of the mixture 4 reaches 3000 cps;
(5) and (3) cooling the mixture 4 obtained in the step (4) to 40 ℃, adding antioxidant BHT, dimethyl carbonate, 120# and acetone, and stirring at the speed of 120 revolutions per minute for 1 hour to obtain the TPR treating agent.
Example 5 an environmentally friendly high performance hydrolysis and aging resistant TPR treatment agent by composite grafting
The TPR treating agent provided by the embodiment is composed of the following raw materials in parts by weight: 60 parts of styrene-butadiene rubber, 50 parts of butadiene-acrylonitrile rubber, 90 parts of chloroprene rubber, 50 parts of acetone, 200 parts of butanone, 630 parts of methylcyclohexane, 400 parts of ethyl acetate, 560 parts of dimethyl carbonate, 120#320 parts of methyl methacrylate, 25 parts of tripropylene glycol diacrylate, 0.8 part of dibenzoyl peroxide and 2.0 parts of antioxidant BHT.
The preparation method of the TPR treating agent comprises the following steps:
(1) firstly, butanone, ethyl acetate and methylcyclohexane are mixed and stirred at the stirring speed of 400 revolutions per minute for 10 minutes to obtain a mixture 1;
(2) adding styrene butadiene rubber into the mixture 1 obtained in the step (1) and stirring at the speed of 650 revolutions per minute and the temperature of 55 ℃ for 2-4 hours to obtain a mixture 2;
(3) adding 0.3 part of dibenzoyl peroxide into the mixture 2 obtained in the step (2), stirring at the speed of 50 revolutions per minute and the temperature of 82 ℃ for 15 minutes, then dropwise adding methyl methacrylate for reaction, wherein the dropwise adding time is 0.5 hour and the reaction time is 2.5 hours, and obtaining a mixture 3;
(4) adding tripropylene glycol diacrylate and 0.5 part of dibenzoyl peroxide into the mixture 3 obtained in the step (3), stirring at the speed of 50 revolutions per minute at the temperature of 82 ℃ for 2 hours to obtain a mixture 4, and considering that the reaction is finished when the viscosity of the mixture 4 reaches 2000 cps;
(5) and (3) cooling the mixture 4 obtained in the step (4) to 35 ℃, adding antioxidant BHT, dimethyl carbonate, 120# and acetone, and stirring at the speed of 110 revolutions per minute for 1 hour to obtain the TPR treating agent.
Comparative example 1
The TPR treatment agent is different from the TPR treatment agent in example 5, and consists of the following raw materials in parts by weight: 45 parts of styrene-butadiene rubber, 45 parts of butadiene-acrylonitrile rubber, 70 parts of chloroprene rubber, 20 parts of acetone, 165 parts of butanone, 720 parts of methylcyclohexane, 240 parts of ethyl acetate, 450 parts of dimethyl carbonate, 120#200 parts of methyl methacrylate, 80 parts of methyl methacrylate, 15 parts of tripropylene glycol diacrylate, 0.3 part of dibenzoyl peroxide and 1.2 parts of antioxidant BHT. Wherein 0.1 part of dibenzoyl peroxide is used in the step (3), and 0.2 part of dibenzoyl peroxide is used in the step (4).
The rest of the raw material sources and the preparation method are the same as those of the example 5.
Comparative example 2
The TPR treatment agent is different from the TPR treatment agent in example 5, and consists of the following raw materials in parts by weight: 100 parts of styrene-butadiene rubber, 80 parts of butadiene-acrylonitrile rubber, 110 parts of chloroprene rubber, 80 parts of acetone, 240 parts of butanone, 450 parts of methylcyclohexane, 550 parts of ethyl acetate, 650 parts of dimethyl carbonate, 450 parts of 120#, 170 parts of methyl methacrylate, 50 parts of tripropylene glycol diacrylate, 1.8 parts of dibenzoyl peroxide and 2.9 parts of antioxidant BHT. Wherein 1.1 parts of dibenzoyl peroxide is used in the step (3), and 0.7 parts of dibenzoyl peroxide is used in the step (4).
The rest of the raw material sources and the preparation method are the same as those of the example 5.
Comparative example 3
The difference from example 5 is that a TPR treatment agent was prepared by stirring at 45 ℃ in the step (2) and at 65 ℃ in the steps (3) and (4).
The rest of the raw material sources and the preparation method are the same as those of the example 5.
Comparative example 4
The difference from example 5 is that a TPR treatment agent was prepared by stirring at 65 ℃ in the step (2) and 95 ℃ in the steps (3) and (4).
The rest of the raw material sources and the preparation method are the same as those of the example 5.
Comparative example 5
The TPR treating agent comprises the following raw materials: styrene butadiene rubber, butadiene cyanide rubber, chloroprene rubber, acetone, butanone, methylcyclohexane, ethyl acetate, dimethyl carbonate, 120#, methyl methacrylate, tripropylene glycol diacrylate, dibenzoyl peroxide and antioxidant BHT.
Wherein the weight ratio of butanone, methylcyclohexane and ethyl acetate was 1:2.0:1.1 (the total weight of butanone, methylcyclohexane and ethyl acetate was the same as in example 5).
The sources and contents of other raw materials and the preparation method are the same as those of the example 5.
Comparative example 6
The TPR treating agent comprises the following raw materials: styrene butadiene rubber, butadiene cyanide rubber, chloroprene rubber, acetone, butanone, methylcyclohexane, ethyl acetate, dimethyl carbonate, 120#, methyl methacrylate, tripropylene glycol diacrylate, dibenzoyl peroxide and antioxidant BHT.
Wherein the weight ratio of butanone, methylcyclohexane and ethyl acetate was 1:4.5:2.5 (the total weight of butanone, methylcyclohexane and ethyl acetate was the same as in example 5).
The sources and contents of other raw materials and the preparation method are the same as those of the example 5.
Comparative example 7
The TPR treating agent comprises the following raw materials: styrene butadiene rubber, butadiene cyanide rubber, chloroprene rubber, acetone, butanone, methylcyclohexane, ethyl acetate, dimethyl carbonate, 120#, methyl methacrylate, tripropylene glycol diacrylate, dibenzoyl peroxide and antioxidant BHT.
Wherein the weight ratio of dimethyl carbonate to 120# was 1:1 (the total weight of dimethyl carbonate and 120# was the same as in example 5).
The sources and contents of other raw materials and the preparation method are the same as those of the example 5.
Comparative example 8
The TPR treating agent comprises the following raw materials: styrene butadiene rubber, butadiene cyanide rubber, neoprene acetone, butanone, methylcyclohexane, ethyl acetate, dimethyl carbonate, 120#, methyl methacrylate, tripropylene glycol diacrylate, dibenzoyl peroxide and antioxidant BHT.
Wherein the weight ratio of dimethyl carbonate to 120# was 2.6:1 (the total weight of dimethyl carbonate and 120# was the same as in example 5).
The sources and contents of other raw materials and the preparation method are the same as those of the example 5.
Comparative example 9
Example 20 in patent CN 103396748B.
Test experiments:
1. the TPR treatment agents prepared in each of examples 1 to 5 and comparative examples 1 to 9 were subjected to adhesion property tests in which initial adhesion, peel strength, shear strength and thermal aging resistance were carried out in accordance with test standards GB-19340-.
Table 1:
as can be seen from Table 1, the TPR treatment agent prepared in the examples of the present invention is superior to the domestic equivalent in initial adhesion, peel strength, shear strength and thermal aging resistance, the comparative examples 1 to 8 have parameter ranges outside the protection range of the present application, the TPR treatment agent prepared by the tests has properties lower than those of the examples, the comparative example 9 is the prior art, and the performance tests have properties lower than those of the TPR treatment agent prepared by the present application under the unified standard.
2. The TPR treatment agents prepared in examples 1-5 and comparative examples 1-9 were tested for yellowing resistance, standard test pieces prepared in GB-19340-:
table 2:
as can be seen from Table 2, the TPR treatment agent prepared by the invention has a yellow resistance grade of 3.5 after 12 hours of UV irradiation, which is superior to 3.0 grade of domestic products. Then, along with the increase of the irradiation time, the yellow resistance grade of the product is changed into 3.0 grade, which is consistent with the domestic products of the same industry. Comparative examples 1-8, which are outside the scope of the present application, all tested to produce TPR treatments having lower yellowing resistance than the examples, and comparative example 9, which is prior art, were compared to produce TPR treatments having lower yellowing resistance than the TPR treatments produced herein, under the same criteria.
3. The TPR treatment agents prepared in examples 1-5 and comparative examples 1-9 were tested for hydrolysis resistance, standard test pieces prepared in GB-19340-:
table 3:
as can be seen from Table 3, the TPR treating agent prepared by the method is found to be superior to domestic products in the performance tests of the peeling strength before hydrolysis, the peeling strength after hydrolysis for 2d, the peeling strength after hydrolysis for 5d and the peeling strength after hydrolysis for 7 d. Comparative examples 1-8, which are outside the scope of the present application, were tested to show that the properties of the TPR treatment prepared are lower than those of the examples, and comparative example 9, which is prior art, were compared under a uniform standard to show that the properties of the TPR treatment prepared are also lower than those of the TPR treatment prepared in the present application.
Claims (7)
1. An environment-friendly high-performance hydrolysis-resistant and aging-resistant TPR treating agent grafted compositely, which is characterized in that:
the TPR treating agent comprises the following raw materials in parts by weight: 50-90 parts of styrene-butadiene rubber, 40-70 parts of nitrile-butadiene rubber, 80-100 parts of chloroprene rubber, 30-70 parts of acetone, 230 parts of butanone 170-;
the weight ratio of the butanone to the methylcyclohexane to the ethyl acetate is 1:2.5-4.0: 1.5-2.1; the weight ratio of the dimethyl carbonate to the 120# is 1.5-2.0: 1.
2. The TPR treatment agent according to claim 1, characterized in that:
the TPR treating agent comprises the following raw materials in parts by weight: 55-80 parts of styrene-butadiene rubber, 50-60 parts of nitrile-butadiene rubber, 80-100 parts of chloroprene rubber, 40-60 parts of acetone, 220 parts of butanone 180-.
3. The TPR treatment agent according to claim 1, characterized in that: the terminator is one or more of antioxidant BHT, antioxidant 1076, antioxidant B215, antioxidant B225, antioxidant 245, antioxidant 1098 and antioxidant 1010.
4. The method for preparing the TPR treatment agent according to any one of claims 1 to 3, comprising the steps of:
(1) firstly, mixing and stirring butanone, ethyl acetate and methylcyclohexane to obtain a mixture 1;
(2) adding styrene butadiene rubber, nitrile butadiene rubber and chloroprene rubber into the mixture 1 obtained in the step (1) and stirring to obtain a mixture 2;
(3) adding dibenzoyl peroxide into the mixture 2 obtained in the step (2), stirring, and then dropwise adding methyl methacrylate to react to obtain a mixture 3;
(4) adding tripropylene glycol diacrylate and dibenzoyl peroxide into the mixture 3 obtained in the step (3) and stirring to obtain a mixture 4;
(5) and (4) cooling the mixture 4 obtained in the step (4), adding a terminator, dimethyl carbonate, 120# and acetone, and stirring to obtain the TPR treating agent.
5. The method of claim 4, wherein: the stirring speed in the step (1) is 350-450 r/min, and the time is 10-15 min.
6. The method of claim 4, wherein: the stirring speed in the step (2) is 550-750 revolutions per minute, the temperature is 51-59 ℃, and the time is 2-4 hours.
7. The method of claim 4, wherein: in the step (3), the stirring speed is 30-70 r/min, the temperature is 72-88 ℃, and the time is 15 min.
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|---|---|---|---|---|
| CN1919886A (en) * | 2006-09-06 | 2007-02-28 | 江苏工业学院 | Method of palliating degradation degree in polypropylene fusion graft process |
| CN105176443A (en) * | 2015-10-13 | 2015-12-23 | 广东三和化工科技有限公司 | Solvent type rubber adhesive and preparation method thereof |
| CN105238298A (en) * | 2015-09-25 | 2016-01-13 | 安徽大松树脂有限公司 | High-performance modified chloroprene rubber adhesive |
| CN109294494A (en) * | 2018-10-09 | 2019-02-01 | 广东裕田霸力科技股份有限公司 | A kind of high-performance environment protection type neoprene adhesive by compound grafting |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03296584A (en) * | 1990-04-17 | 1991-12-27 | Sekisui Chem Co Ltd | Solvent base pressure-sensitive adhesive |
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|---|---|---|---|---|
| CN1919886A (en) * | 2006-09-06 | 2007-02-28 | 江苏工业学院 | Method of palliating degradation degree in polypropylene fusion graft process |
| CN105238298A (en) * | 2015-09-25 | 2016-01-13 | 安徽大松树脂有限公司 | High-performance modified chloroprene rubber adhesive |
| CN105176443A (en) * | 2015-10-13 | 2015-12-23 | 广东三和化工科技有限公司 | Solvent type rubber adhesive and preparation method thereof |
| CN109294494A (en) * | 2018-10-09 | 2019-02-01 | 广东裕田霸力科技股份有限公司 | A kind of high-performance environment protection type neoprene adhesive by compound grafting |
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